CN113036153A - Copper-based current collector for inducing preferential transverse deposition of lithium metal negative electrode and preparation method and application thereof - Google Patents

Copper-based current collector for inducing preferential transverse deposition of lithium metal negative electrode and preparation method and application thereof Download PDF

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CN113036153A
CN113036153A CN202110264303.4A CN202110264303A CN113036153A CN 113036153 A CN113036153 A CN 113036153A CN 202110264303 A CN202110264303 A CN 202110264303A CN 113036153 A CN113036153 A CN 113036153A
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copper
current collector
lithium metal
zinc
deposition
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边秀房
杨映晖
王军长
孙辰翊
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Shandong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a copper-based current collector for inducing a lithium metal negative electrode to preferentially and transversely deposit, and a preparation method and application thereof. The dense zinc oxide layer of the current collector reduces the charge density in the parallel direction and prevents the deposition growth of lithium metal in the vertical direction of the current collector. The lithium-philic copper nanosheet array and the zinc oxide layer act synergistically to induce preferential transverse deposition of lithium metal and inhibit generation of lithium dendrites, so that the safety and the cycle life of the lithium metal battery are improved.

Description

Copper-based current collector for inducing preferential transverse deposition of lithium metal negative electrode and preparation method and application thereof
Technical Field
The invention relates to a copper-based current collector for inducing preferential transverse deposition of a lithium metal negative electrode and a preparation method and application thereof, belonging to the technical field of batteries.
Technical Field
The modern society is on new energy automobiles andenergy storage has raised higher and higher requirements, and the conventional lithium ion battery using the graphite cathode has gradually failed to meet the requirements, so a new generation of battery system with higher energy density is urgently needed in various fields. The lithium metal has high theoretical specific capacity (3680mAh/g), lowest reduction potential (-3.04V vs. SHE) and extremely small density (0.534 g/cm)3) It is an ideal material for the negative electrode of lithium battery. In this background, the development of lithium metal negative electrodes is an indispensable and important link in strategic deployment of next-generation battery systems.
However, lithium metal negative electrodes still present quite serious problems in practical use, among which lithium dendrites induced by uneven deposition of lithium metal are the most problematic. The lithium dendrite not only causes 'dead lithium', causes repeated growth of an SEI film and rapid consumption of an electrolyte, reduces the performance of a battery and shortens the service life of the battery, but also pierces a separator to cause short circuit of the battery and cause thermal runaway, and in severe cases, can cause serious accidents such as fire or explosion.
The current collector with the three-dimensional structure is constructed, so that the effective deposition area of lithium metal can be remarkably increased, the local charge density is reduced, and the generation of lithium dendrites can be effectively inhibited. Various lithium metal negative electrode three-dimensional current collectors and preparation methods thereof have been disclosed, but these methods do not induce or limit the deposition direction of lithium metal, and thus have limited effects on improving the performance and prolonging the life of a lithium metal negative electrode.
For example, chinese patent document CN110828828A discloses a 3D porous zinc-loaded current collector, which includes a 3D porous current collector and metallic zinc compounded on a skeleton of the 3D porous current collector. The invention innovatively compounds metal zinc on the framework of the 3D porous current collector; the current collector with the structure can effectively maintain the stability of a framework in the process of depositing sodium or potassium metal; meanwhile, the metal zinc uniformly distributed on the pore framework can induce the nucleation of metal sodium or potassium, so that the effective specific surface area of the 3D current collector is fully utilized in the sodium or potassium deposition process, the dendrite-free sodium or potassium deposition and the long cycle life are realized, but the 3D porous zinc load current collector cannot induce or limit the deposition direction of a metal cathode.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a copper-based current collector for inducing preferential transverse deposition of a lithium metal negative electrode, which can induce preferential transverse deposition of lithium metal and is used for improving the electrochemical performance of the lithium metal negative electrode.
The second purpose of the invention is to provide a preparation method of the copper-based current collector for inducing preferential lateral deposition of the lithium metal negative electrode. The method has low cost, amplification and strong controllability.
A third object of the present invention is to provide the use of a copper-based current collector to induce preferential lateral deposition of a lithium metal negative electrode.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a copper-based current collector for inducing preferential transverse deposition of a lithium metal negative electrode is characterized in that a zinc oxide layer and a copper nanosheet array are grown in situ or modified in an ectopic mode on the surface of a copper-based foil, the zinc oxide layer is tiled on the surface of the copper-based foil, and the copper nanosheet array vertically penetrates through the zinc oxide layer to be connected with a substrate of the copper-based foil.
According to the invention, the thickness of the zinc oxide layer is preferably 100 to 2000 nm.
According to the invention, the thickness of the copper nanosheet array is 10-80 nm, and the height of the copper nanosheet array is 0.5-5 μm.
The zinc oxide layer is a dense zinc oxide layer having poor conductivity. The copper nanosheet array is a copper nanosheet array with good conductivity.
According to the invention, preferably, the surface of the copper nanosheet array is modified with zinc oxide nanoparticles, and the particle size of the zinc oxide nanoparticles is less than or equal to 10 nm.
The current collector zinc oxide layer is tiled on the surface of the copper-based foil, and the zinc oxide layer is parallel to the direction of the current collector, so that the charge density in the parallel direction is reduced, and the growth of lithium metal in the vertical direction is inhibited; the copper nanosheet array vertically penetrates through the zinc oxide layer to be connected with the copper-based foil substrate, the copper nanosheet is good in conductivity and modified with lithium-philic oxide particles (zinc oxide), and lithium metal is induced to be uniformly deposited on the surface of the copper nanosheet and transversely expanded along the parallel direction of the current collector, so that a relatively flat lithium metal negative electrode surface is formed, and dendritic-crystal-free deposition of the lithium metal negative electrode is realized.
The preparation method of the copper-based current collector for inducing the preferential transverse deposition of the lithium metal negative electrode comprises the following steps:
s1, surface treatment of copper-zinc base foil: sequentially removing surface dirt and oxide impurities from the copper-zinc-based foil by using absolute ethyl alcohol and dilute hydrochloric acid, then washing the copper-zinc-based foil clean by using deionized water and absolute ethyl alcohol, and drying the copper-zinc-based foil at room temperature for later use;
s2, preparing a precursor by a wet chemical method: preparing an ammonia water solution, precooling the solution until the temperature of the solution reaches a certain temperature, contacting the single side of the copper-zinc-based foil treated in the step S1 with the ammonia water solution, standing for reaction, taking out the copper-zinc-based foil, cleaning and drying for later use;
s3, heat treatment: h the copper-zinc-based foil treated in the step S2 is treated2And carrying out heat treatment in the/Ar mixed atmosphere, and cooling to room temperature to obtain the copper-based current collector with the surface in-situ grown copper nanosheet array and the zinc oxide layer.
The zinc element in the copper-zinc-based foil used by the invention is distributed uniformly or non-uniformly.
According to a preferred embodiment of the present invention, in step S1, the concentration of the dilute hydrochloric acid is 0.1-0.3 mol/L.
According to the invention, the concentration of the ammonia water solution in the step S2 is preferably 0.01-0.05 mol/L.
According to the preferable method, in the step S2, the pre-cooling is performed at 0-10 ℃ so that the temperature of the ammonia water solution reaches 0-10 ℃.
According to the preferable method, in the step S2, the standing reaction is carried out at the temperature of 0-10 ℃ for 20-40 h.
According to the present invention, in step S3, the heat treatment temperature is preferably 200 to 600 ℃.
Preferably, in step S3, the heat treatment time is 20-60 min.
According to a preferred embodiment of the invention, step S3, H2H in mixed Ar atmosphere2The concentration is 5-10%.
According to the preferable method, in the step S3, the heating rate of the heat treatment is 3-8 ℃/min, and the cooling rate of the cooling to the room temperature is 3-8 ℃/min.
The method comprises the steps of preparing a precursor by using a wet chemical method by using a copper-zinc alloy as a raw material, then carrying out heat treatment to obtain a current collector with a zinc oxide layer and a copper nanosheet array in-situ growing or ex-situ modification on the surface of a copper-based foil, wherein an ammonia water is used as a solvent of the wet chemical method, when the copper-zinc alloy is soaked in the ammonia water, metal zinc reacts with the ammonia water to generate zinc oxide nanoparticles, metal copper reacts with the ammonia water to generate copper hydroxide, the copper hydroxide grows in an anisotropic manner to form a nanosheet structure, and after heat treatment in a hydrogen atmosphere, the copper hydroxide is dehydrated to generate copper oxide which is reduced into a copper simple substance by hydrogen to form.
A copper-based current collector for inducing preferential transverse deposition of a lithium metal negative electrode is applied to a lithium ion battery to prepare an electrode plate.
According to the invention, the preferable specific application method is as follows:
depositing lithium metal into the current collector by adopting an electrochemical deposition method, wherein the deposition current density is 0.1-5 mA/cm2The deposition capacity is 0.5-5 mAh/cm2。
An electrode pole piece, contain above-mentioned current collector in the electrode pole piece.
A battery comprises the current collector or the electrode plate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the current collector zinc oxide layer is tiled on the surface of the copper-based foil, and the zinc oxide layer is parallel to the direction of the current collector, so that the charge density in the parallel direction is reduced, and the growth of lithium metal in the vertical direction is inhibited; the copper nanosheet array penetrates through the zinc oxide layer to be perpendicular to the copper-based foil substrate, the copper nanosheet is good in conductivity and modified with lithium-philic oxide particles (zinc oxide), and lithium metal is induced to be uniformly deposited on the surface of the nanosheet and transversely expanded along the parallel direction of the current collector, so that a relatively flat lithium metal negative electrode surface is formed, and dendritic-free deposition of the lithium metal negative electrode is realized.
2. The copper-zinc-based foil raw material used in the invention is environment-friendly, low in price and wide in source; the wet chemical method and the heat treatment process used for preparation have the advantages of simple operation, extremely low requirement on equipment and easy amplification and industrial application.
3. The copper-based current collector can induce lithium metal to be preferentially and transversely deposited on the current collector, so that a flat deposition surface is formed, the generation of lithium dendrites is inhibited, the safety of a lithium metal negative electrode is improved, and the cycle life of the lithium metal negative electrode is prolonged.
Drawings
Fig. 1 is a surface topography plot of a copper-based current collector inducing preferential lateral deposition of lithium metal in example 1;
FIG. 2 is a topographical view of a copper-based current collector that induces preferential lateral deposition of lithium metal in example 1;
fig. 3 is a surface topography of a copper-based current collector prepared in comparative example 1;
fig. 4 is a surface topography of a copper-based current collector prepared in comparative example 2;
FIG. 5 is a graph of the deposition profile of lithium metal on a planar copper-based current collector in Experimental example 1;
fig. 6 is a deposition profile of lithium metal on a current collector that induces preferential lateral deposition thereof in experimental example 1;
fig. 7 is the coulombic efficiency of lithium metal deposition/exfoliation on planar copper current collectors and current collectors that can induce preferential lateral deposition thereof, respectively, in experimental example 2;
FIG. 8 shows the results of experimental example 3, wherein the cell density was 2mA/cm2The current density of the current is measured for each 0.5h of charge-discharge cycle to obtain a curve;
fig. 9 is a graph of cycle performance at 2C rate for the full cell assembled in example 2.
Detailed Description
In order to better explain the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention will be further described in detail with reference to the accompanying drawings in the embodiments of the present invention. The following examples are only some examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
A preparation method of a copper-based current collector for inducing preferential lateral deposition of a lithium metal negative electrode comprises the following steps:
s1, cleaning the surface of the copper zinc-based foil: the commercial brass foil is cleaned by using absolute ethyl alcohol for three times in an ultrasonic mode, the surface of the commercial brass foil is wiped by using dust-free paper, then the commercial brass foil is soaked in 0.1mol/L dilute hydrochloric acid for 30 seconds to remove oxide impurities on the surface of the foil, then deionized water and absolute ethyl alcohol are used for washing the foil, and the foil is dried at room temperature for later use, the mark of the used brass foil is H62, the thickness of the foil is 20 mu m, and the price of the foil is low.
S2, preparing a precursor by a wet chemical method: preparing an ammonia water solution with the concentration of 0.03mol/L by using deionized water and strong ammonia water, then precooling at 2-8 ℃, after the solution temperature reaches a specified temperature, contacting one side of the copper-zinc-based foil treated by S1 with the ammonia water solution, standing for 36h at 2-8 ℃, taking out, washing with deionized water and absolute ethyl alcohol, and drying at room temperature for later use.
S3, heat treatment: h the copper-zinc-based foil treated in the step S2 is treated2Mixed atmosphere of/Ar (H)2The concentration is 5-7%), and cooling to room temperature to obtain a copper-based current collector with a copper nanosheet array and a zinc oxide layer growing in situ on the surface; the heat treatment temperature is 360 deg.C, and the heat treatment time is 30 min.
Fig. 1 is a scanning electron micrograph of the surface of the copper-based current collector obtained in example 1, and fig. 2 is a scanning electron micrograph of the cross section of the copper-based current collector obtained in example 1.
As can be seen from fig. 1 and 2, the surface of the current collector has a zinc oxide layer and a copper nanosheet array, the height of the copper nanosheet array modified by lithium-philic zinc oxide nanoparticles is about 1.5 μm, the thickness of the copper nanosheet is about 30-50 nm, and the thickness of the dense zinc oxide layer is about 800 nm.
Comparative example 1
The method for preparing the copper-based current collector is the same as that in example 1, except that:
in step S2, the ammonia water was used at a concentration of 0.005 mol/L.
Fig. 3 is a scanning electron micrograph of the surface of the copper-based current collector obtained in the present comparative example.
As can be seen from fig. 3, when the concentration of ammonia water is too low, the copper nanosheets are unevenly distributed on the surface of the current collector, and the zinc oxide layer has cracks.
Comparative example 2
The method for preparing the copper-based current collector is the same as that in example 1, except that:
in step S2, the ammonia water was used at a concentration of 0.1 mol/L.
Fig. 4 is a scanning electron micrograph of the surface of the copper-based current collector obtained in the present comparative example.
As can be seen from fig. 4, when the concentration of the ammonia water is too high, the number of the copper nanosheets is reduced, and a tightly arranged array structure cannot be formed on the surface of the current collector.
Experimental example 1
This experimental example compares the deposition morphology of lithium metal on a planar copper current collector with that on a copper-based current collector which can induce preferential lateral deposition thereof.
Electrodeposition of lithium metal is performed by assembling the half-cells. In the half cell, commercial lithium foil was used as the negative electrode, 1M LiTFSI/DOL + DME (1:1 by volume) + 1% LiNO3Is electrolyte, PP is diaphragm, and current collector is anode. The cell assembly was carried out in a glove box protected with an argon atmosphere having a water oxygen value below 0.01 ppm. The half cell left for 24h is charged and discharged for five times in the current density of 50 muA and the voltage range of 0-1V for activation treatment, and then the voltage is 1mA/cm2Is discharged for two hours at the current density of (1) to carry out electrodeposition. The cell that completed the electrodeposition process was disassembled in an argon atmosphere glove box. And (3) washing the residual electrolyte on the surface of the lithium metal composite cathode by using ethylene glycol dimethyl ether (DME), drying, and transferring to a scanning electron microscope sample chamber under the protection of argon atmosphere for appearance observation.
FIG. 5 is a deposition profile of lithium metal on a planar copper current collector, and FIG. 6 is a deposition profile of lithium metal on a copper-based current collector capable of inducing preferential lateral deposition of lithium metal with a deposition capacity of 2mAh/cm2. It can be seen that the deposition of lithium metal on the planar copper current collector presents thicker whisker-like dendrites, no lithium dendrites are generated on the surface of the copper-based current collector which can induce the preferential transverse deposition of lithium metal, and the deposition surface of the lithium metal is quite flat.
Experimental example 2
This experimental example compares the coulombic efficiencies of lithium metal deposition/dissolution on planar copper current collectors and copper-based current collectors that can induce preferential lateral deposition of lithium metal, respectively.
This example was tested in a half cell, which was assembled in the same manner as in example 1. The coulombic efficiency was measured using a neomycin 5V/10mA cell tester. The deposition capacity is 1mAh/cm2The peel cut-off voltage was 1V. The current density for deposition and stripping was 1mA/cm2。
Fig. 7 is a coulombic efficiency curve of the half cell obtained in experimental example 2.
Since the deposition of lithium metal is more even on a copper-based current collector capable of inducing preferential lateral deposition of lithium metal, the formation of lithium dendrites is suppressed, and the generation of dead lithium is reduced, higher coulombic efficiency can be achieved.
Experimental example 3
This experimental example compares the performance of a lithium symmetric battery using a planar copper current collector and a copper-based current collector that can induce preferential lateral deposition of lithium metal, respectively.
Lithium is first pre-deposited onto the current collector in the half cell. The assembly method of the half-cell used for predeposition is the same as that of the experimental example 1, after standing for 24 hours, the two half-cells are charged and discharged for five times in the current density of 50 muA and the voltage range of 0-1V for activation treatment, and then the voltage is 0.2mA/cm2Discharging at a current density of 5mAh/cm to carry out electrodeposition2。
The lithium metal composite electrode obtained after the electrodeposition is used as a positive electrode and a negative electrode, and 1M LiTFSI/DOL + DME (volume ratio is 1:1) + 1% LiNO3The electrolyte and PP were separators, and the cells were assembled in a glove box under argon atmosphere. The battery is left for 24 hours and then is placed at 2mA/cm2The current density of (A) was measured, each timeThe time of cyclic charge and discharge is 0.5 h.
Fig. 8 is a cycle test curve of the symmetrical battery obtained in experimental example 3.
Since the formation of lithium dendrites is suppressed and the deposition of lithium metal is more even on a copper-based current collector capable of inducing preferential lateral deposition of lithium metal, a symmetric battery assembled based on a copper-based current collector capable of inducing preferential lateral deposition of lithium metal exhibits a lower lithium deposition/stripping overpotential and a longer cycle life, which exceeds 1500 h.
Example 2
A copper-based current collector for inducing preferential lateral deposition of a lithium metal negative electrode for use in a lithium metal battery.
Based on the copper-based current collector capable of inducing preferential lateral deposition of lithium metal prepared in example 1, a lithium metal composite electrode was prepared based on the method of pre-depositing lithium in experimental example 3, and used as a negative electrode of a full cell, and the capacity of the pre-deposited lithium was 5mAh/cm2. Commercial LiCoO for lithium ion batteries2The pole piece is used as a positive electrode, PP is used as a diaphragm, and 1M LiPF6(iii) using/EC + DEC + DMC (1:1:1) + 5% FEC as electrolyte, assembling button full cell in argon atmosphere glove box with water oxygen value lower than 0.01 ppm. The cycle performance was tested.
Selected LiCoO2The loading amount of the positive electrode was 9.62mg/cm2The nominal specific capacity is 145 mAh/g. After the full cell was left to stand for 24 hours, a constant current charge and discharge test was performed at a 2C rate.
Fig. 9 is a cycle performance graph of the full cell in example 2 at a large rate of 2C. After 100 cycles, the coulombic efficiency of the cell was still close to 100% and there was no significant capacity fade.

Claims (10)

1. A copper-based current collector for inducing preferential transverse deposition of a lithium metal negative electrode is characterized in that a zinc oxide layer and a copper nanosheet array are grown in situ or modified in an ectopic mode on the surface of a copper-based foil, the zinc oxide layer is tiled on the surface of the copper-based foil, and the copper nanosheet array vertically penetrates through the zinc oxide layer to be connected with a substrate of the copper-based foil.
2. The copper-based current collector for inducing preferential lateral deposition of a lithium metal negative electrode according to claim 1, wherein the thickness of the zinc oxide layer is 100-2000 nm, the thickness of the copper nanosheets of the copper nanosheet array is 10-80 nm, and the height of the copper nanosheet array is 0.5-5 μm.
3. The copper-based current collector for inducing preferential lateral deposition of a lithium metal negative electrode according to claim 1, wherein zinc oxide nanoparticles are modified on the surface of the copper nanosheets of the copper nanosheet array.
4. A preparation method of a copper-based current collector for inducing preferential lateral deposition of a lithium metal negative electrode comprises the following steps:
s1, surface treatment of copper-zinc base foil: sequentially removing surface dirt and oxide impurities from the copper-zinc-based foil by using absolute ethyl alcohol and dilute hydrochloric acid, then washing the copper-zinc-based foil clean by using deionized water and absolute ethyl alcohol, and drying the copper-zinc-based foil at room temperature for later use;
s2, preparing a precursor by a wet chemical method: preparing an ammonia water solution, precooling the solution until the temperature of the solution reaches a certain temperature, contacting the single side of the copper-zinc-based foil treated in the step S1 with the ammonia water solution, standing for reaction, taking out the copper-zinc-based foil, cleaning and drying for later use;
s3, heat treatment: h the copper-zinc-based foil treated in the step S2 is treated2And carrying out heat treatment in the/Ar mixed atmosphere, and cooling to room temperature to obtain the copper-based current collector with the surface in-situ grown copper nanosheet array and the zinc oxide layer.
5. The method according to claim 4, wherein in step S1, the concentration of the dilute hydrochloric acid is 0.1 to 0.3 mol/L.
6. The preparation method according to claim 4, wherein in step S2, the concentration of the aqueous ammonia solution is 0.01-0.05 mol/L, the pre-cooling is pre-cooling at 0-10 ℃ to make the temperature of the aqueous ammonia solution reach 0-10 ℃, and the standing reaction is a standing reaction at 0-10 ℃ for 20-40 h.
7. The method according to claim 4, wherein in step S3, the heat treatment temperature is 200-600 ℃ and the heat treatment time is 20-60 min.
8. The method of claim 4, wherein step S3, H2H in mixed Ar atmosphere2The concentration is 5-10%, the heating rate of the heat treatment is 3-8 ℃/min, and the cooling rate of the temperature to room temperature is 3-8 ℃/min.
9. An electrode sheet comprising the current collector of claim 1.
10. A battery comprising the current collector of claim 1 or the electrode sheet of claim 9.
CN202110264303.4A 2021-03-11 2021-03-11 Copper-based current collector for inducing preferential transverse deposition of lithium metal negative electrode and preparation method and application thereof Pending CN113036153A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113659282A (en) * 2021-08-17 2021-11-16 哈尔滨工业大学 Oxide coating with oxygen defect for inhibiting lithium dendrite and preparation method thereof
CN113782749A (en) * 2021-08-24 2021-12-10 蜂巢能源科技(无锡)有限公司 Cathode for all-solid-state battery, preparation method of cathode and all-solid-state battery
CN114400331A (en) * 2022-03-03 2022-04-26 电子科技大学 Preparation method of negative current collector capable of improving lithium metal cycle stability
CN115036513A (en) * 2022-06-27 2022-09-09 澳门大学 Three-dimensional current collector, preparation method thereof, lithium metal negative electrode and lithium metal battery
CN115863660A (en) * 2022-12-09 2023-03-28 江苏正力新能电池技术有限公司 Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
官福荣: "《无机元素化学》", 31 July 2019 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113659282A (en) * 2021-08-17 2021-11-16 哈尔滨工业大学 Oxide coating with oxygen defect for inhibiting lithium dendrite and preparation method thereof
CN113782749A (en) * 2021-08-24 2021-12-10 蜂巢能源科技(无锡)有限公司 Cathode for all-solid-state battery, preparation method of cathode and all-solid-state battery
CN114400331A (en) * 2022-03-03 2022-04-26 电子科技大学 Preparation method of negative current collector capable of improving lithium metal cycle stability
CN115036513A (en) * 2022-06-27 2022-09-09 澳门大学 Three-dimensional current collector, preparation method thereof, lithium metal negative electrode and lithium metal battery
CN115863660A (en) * 2022-12-09 2023-03-28 江苏正力新能电池技术有限公司 Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof

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